US4693749A - Cement reinforcement - Google Patents

Cement reinforcement Download PDF

Info

Publication number
US4693749A
US4693749A US06/811,843 US81184385A US4693749A US 4693749 A US4693749 A US 4693749A US 81184385 A US81184385 A US 81184385A US 4693749 A US4693749 A US 4693749A
Authority
US
United States
Prior art keywords
fiber
coated
cement
phenyleneterephthalamide
units
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US06/811,843
Other languages
English (en)
Inventor
David M. Gale
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US06/811,843 priority Critical patent/US4693749A/en
Assigned to E. I. DU PONT DE NEMOURS AND COMPANY reassignment E. I. DU PONT DE NEMOURS AND COMPANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: GALE, DAVID M.
Priority to CA000525496A priority patent/CA1276087C/en
Priority to JP61300176A priority patent/JPS62158149A/ja
Priority to AU66736/86A priority patent/AU585790B2/en
Priority to DK618286A priority patent/DK618286A/da
Priority to KR860010934A priority patent/KR870005928A/ko
Priority to DE8686309960T priority patent/DE3669705D1/de
Priority to EP86309960A priority patent/EP0227452B1/en
Publication of US4693749A publication Critical patent/US4693749A/en
Application granted granted Critical
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/38Fibrous materials; Whiskers
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10Coating or impregnating
    • C04B20/1051Organo-metallic compounds; Organo-silicon compounds, e.g. bentone
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B16/00Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B16/04Macromolecular compounds
    • C04B16/06Macromolecular compounds fibrous
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/503Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core
    • Y10T428/2964Artificial fiber or filament
    • Y10T428/2967Synthetic resin or polymer
    • Y10T428/2969Polyamide, polyimide or polyester

Definitions

  • This invention relates to coated aramid fibers for cement reinforcement and to fiber-reinforced cement products incorporating such fibers.
  • the combination of such coated aramid fibers with a pulp of oriented polyethylene fibrids is particularly useful for this purpose.
  • p-aramid fibers are made more suitable for cement reinforcement by coating them with from 0.25 to 40%, preferably from 0.25 to 10% by weight of an alkyl titanate, or a titanium chelate compound.
  • the aramid fiber is poly-p-phenylene terephthalamide or a copolymer thereof.
  • the invention also includes reinforced cement products containing from 0.1 to 6% by weight of the coated fiber.
  • a pulp of oriented polyethylene fibrids is employed in combination with the coated p-aramid fiber for the cement reinforcement.
  • cement products reinforced with fibers of p-aramids have previously been suggested, however, there is a need for cement products of greater flexural strength and toughness. Applicant has found that this objective is reached by coating the p-aramid fiber with an alkyl titanate or a titanium chelate compound prior to incorporation in the cement.
  • the p-aramid fiber used in the present invention is formed of poly-p-phenyleneterephthalamide prepared from p-phenylene diamine and terephthalic acid or functional equivalents thereof. Better results have been obtained when a copolymer fiber prepared from p-phenylene diamine, terephthalic acid and 2,6-naphthoic acid or functional equivalents thereof is employed. In such copolymers there should be at least 75 mole % terephthalamide and up to 25 mole % of 2,6-naphthalamide units. Certain of the p-aramid fibers are commercially available such as Kevlar® 49 Aramid fiber (E. I. du Pont de Nemours and Company).
  • lactic acid titanate chelate ammonium salt also known as titanium lactate, ammonium salt
  • Ti lactate titanium lactate
  • Other titanates such as the triethanolamine chelate and tetraisopropyl titanate, commercially available as Tyzor® TE and Tyzor TPT from E. I. du Pont de Nemours and Company are also useful.
  • Alkyl (of up to 12 carbon atom length groups) titanates such as tetraisopropyl, tetrabutyl and tetrakis (2-ethylhexyl) titanates may be used but are less preferred.
  • titanates such as tetraisopropyl, tetrabutyl and tetrakis (2-ethylhexyl) titanates may be used but are less preferred.
  • titanates such as tetraisopropyl, tetrabutyl and tetrakis (2-ethylhexyl) titanates may be used but are less preferred.
  • from about 0.25 to 10% by weight of the chelate is coated on the p-aramid yarn from aqueous solution.
  • the yarn is then dried and cut into staple lengths which for cement reinforcement purposes are generally in the range of from 4 to 20 mm. in length, preferably 5-12 mm. in length.
  • Fiber reinforced cement composites were evaluated by determining flexural toughness (also called work-to-break). The test is described in ASTM D-790. Flexural testing is used frequently by the asbestos cement industry as a measure of product performance for sheet products such as roofing tiles, building panels, etc. Cement samples (2.54 cm ⁇ 15.2 cm33 0.5 cm), prepared as described below were tested according to the above ASTM method in 3-point bending in an Instron test machine. A span of 7.6 cm was used in all cases. Test specimens are loaded to failure, and the maximum stress level determined graphically with a chart recorder. Flexural toughness is taken as the integrated area under the stress-strain curve until maximum stress is reached, measured in kJ/sq m (kilojoules per square meter). All samples, including controls were tested in the same way.
  • the "flexural strength” sometimes called modulus of rupture is the point of maximum stress in the above test. It is reported in MPa (megapascals).
  • aqueous solution of the titanium/lactic acid complex was diluted with one or nine parts of distilled water, depending on whether a high or low level of coating was desired.
  • the yarn was a multifilament poly-p-phenyleneterephthalamide yarn having a tensile strength of about 400,000 lb/in 2 and a modulus of about 18 million lb/in 2 .
  • the filament denier was between about 1.7 and 2.5 dtex.
  • the yarn was formed from a copolymer containing about 80 mole % of p-phenyleneterephthalamide units and about 20 mole % of p-phenylene-2,6-naphthalamide units.
  • the yarns were coated by dipping them into the solutions or by passing the yarns over a slotted coating head at 50 yd/min and metering the solutions onto the yarn through a metering pump to produce the desired coating levels. Drying of the yarns was begun by passing them through a heated furnace, over heated rolls or both; furnace/roll temperatures of 100°-200° C. (usually 150° C.) were employed depending on the denier of the yarn and method of application. Conditions were set so as to evaporate most but not all of the solvent water. Final drying was accomplished by transferring the yarns to perforated bobbins and heating them in a vacuum oven at 110° C./20 mm until constant weight was reached (usually overnight). Coating levels were determined by weighing the yarns before and after coating or by calibration of the metering system. Dried yarns were cut into 6 mm staple before use in making cement tiles.
  • fiber reinforced cement composites are prepared which contain Portland cement, or mixtures of Portland cement and silica flour, together with various fibrous synthetic materials. Pulps are prepared by placing the unopened pulp (usually 8 gm) into a home blender with 1 l of water and blending on low speed for about 30-90 seconds (pulp all fluffed up). Opened pulps, thus prepared, are added to a plastic bucket containing about 4 l of water and the coated staple fibers. The mix is dispersed for 5 min with gentle agitation using a vibrating laboratory stirrer. Type 1 Portland cement (200 gm), or a mixture of cement and silica (200 gm total), dispersed into a slurry with 1 l of water, is then added.
  • Flocculation is induced by addition of 4 ml of a 0.1% solution of flocculating agent (Separan A-273 manufactured by Dow Chemical Co.). The entire slurry is then cast into a sheet 33 cm ⁇ 33 cm and approximately 1.5-2 mm thick by pouring into a standard Deckle box paper making mold and dewatering. The resulting sheet is then folded into four layers, trimmed to 15.2 ⁇ 15.2 cm and pressed in a mold for 30 min at 1667 psi.
  • a flocculating agent Separan A-273 manufactured by Dow Chemical Co.
  • Example I tiles are prepared for testing by pre-curing the molded composite (removed from the mold) one day at room temperature at about 100% relative humidity followed by curing in a steam autoclave (about 100 psi) at 160° for 6.5 hrs, whereas Example II tiles are cured for 28 days immersed in saturated lime water.
  • the cured cement tiles are cut into strips 2.54 cm wide with a diamond saw. The strips are re-immersed in lime water and tested wet in 3-point bending to determine flexural toughness. Flexural strength values are given in MPa units and work-to-break toughness, that is the under the stress-strain curve to maximum stress, are given in KJ/sq m.
  • Poly-p-phenylene terephthalamide was cut into 6 mm staple. 8 gm samples were dipped into various coating compositions, removed, drained and kept in an oven at 60° C. overnight. Final sample weights were about 11 gm, indicating that substantial coating had been picked-up by the fiber.
  • cement tiles were prepared from 4 gm of the coated staple, 8 gm of newspulp, and 200 gm of type 1 Portland cement. Testing was conducted as indicated above. This example establishes the usefulness of a variety of titanate-coated aramids for cement reinforcement. Average results are indicated:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Civil Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Cultivation Of Seaweed (AREA)
  • Treatment Of Sludge (AREA)
  • Multicomponent Fibers (AREA)
US06/811,843 1985-12-20 1985-12-20 Cement reinforcement Expired - Lifetime US4693749A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US06/811,843 US4693749A (en) 1985-12-20 1985-12-20 Cement reinforcement
CA000525496A CA1276087C (en) 1985-12-20 1986-12-16 Cement reinforcement
JP61300176A JPS62158149A (ja) 1985-12-20 1986-12-18 セメント強化材
AU66736/86A AU585790B2 (en) 1985-12-20 1986-12-18 Cement reinforcement
DK618286A DK618286A (da) 1985-12-20 1986-12-19 Fiberforstaerkningsmateriale til cementprodukter
KR860010934A KR870005928A (ko) 1985-12-20 1986-12-19 시멘트 보강재
DE8686309960T DE3669705D1 (de) 1985-12-20 1986-12-19 Zementverstaerkung.
EP86309960A EP0227452B1 (en) 1985-12-20 1986-12-19 Cement reinforcement

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US06/811,843 US4693749A (en) 1985-12-20 1985-12-20 Cement reinforcement

Publications (1)

Publication Number Publication Date
US4693749A true US4693749A (en) 1987-09-15

Family

ID=25207745

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/811,843 Expired - Lifetime US4693749A (en) 1985-12-20 1985-12-20 Cement reinforcement

Country Status (8)

Country Link
US (1) US4693749A (ja)
EP (1) EP0227452B1 (ja)
JP (1) JPS62158149A (ja)
KR (1) KR870005928A (ja)
AU (1) AU585790B2 (ja)
CA (1) CA1276087C (ja)
DE (1) DE3669705D1 (ja)
DK (1) DK618286A (ja)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4974522A (en) * 1989-06-09 1990-12-04 Relmech Manufacturing Limited Cold-molded cementitious composites reinforced with surface-modified polyamide fibres and method of preparing same
US4994148A (en) * 1989-03-14 1991-02-19 Shetka Stanley J Pulp press molding method for making products from paper pulp from recycled paper
US5416156A (en) * 1988-10-14 1995-05-16 Revlon Consumer Products Corporation Surface coating compositions containing fibrillated polymer
US5593625A (en) * 1992-08-11 1997-01-14 Phenix Biocomposites, Inc. Biocomposite material and method of making
US5611882A (en) * 1993-08-11 1997-03-18 Phenix Biocomposites, Inc. Board stock and method of manufacture from recycled paper
US5616683A (en) * 1993-01-13 1997-04-01 Hoechst Ag Process for maintaining of improving the mechanical properties of fibers of aromatic copolyamides in alkaline media and shaped articles containing such fibers
WO2000059812A1 (en) 1999-04-07 2000-10-12 Hudson-Sharp Machine Company Conveyor apparatus for conveying stacks of articles
WO2004020358A1 (en) * 2002-08-27 2004-03-11 Laticrete International, Inc. Cement-based thin-set mortar

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK695688D0 (da) * 1988-12-14 1988-12-14 Danaklon As Fibre og materiale indeholdende samme
DE19860335B4 (de) * 1997-12-25 2007-02-22 Chisso Corp. Betonverstärkende Faser
US6753081B1 (en) 2001-02-21 2004-06-22 Forta Corporation Fiber reinforcement material, products made therefrom, and method for making the same
US7168232B2 (en) 2001-02-21 2007-01-30 Forta Corporation Fiber reinforcement material, products made thereform, and method for making the same
JP2006517171A (ja) * 2002-09-25 2006-07-20 ザ インターテック グループ インコーポレイテッド 繊維強化セメント材料

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3616184A (en) * 1968-03-12 1971-10-26 Yasushi Katagiri Titanium dioxide-containing synthetic filament having improved properties textile products made therefrom and method of imparting said improved properties
US3857727A (en) * 1970-10-22 1974-12-31 L Benisek Textile finishing
JPS5562832A (en) * 1978-11-06 1980-05-12 Asahi Chemical Ind Manufacture of fiber reinforced cement product
WO1984003275A1 (en) * 1983-02-23 1984-08-30 Courtaulds Plc Cellulose fibers for cement reinforcement
US4515636A (en) * 1984-08-17 1985-05-07 E. I. Du Pont De Nemours And Company Reinforced cement
JPS60260449A (ja) * 1984-06-08 1985-12-23 帝人株式会社 セメント成型品

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3139313A1 (de) * 1981-10-02 1983-04-21 Bayer Ag, 5090 Leverkusen Verwendung metallisierter aramidfaeden

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3616184A (en) * 1968-03-12 1971-10-26 Yasushi Katagiri Titanium dioxide-containing synthetic filament having improved properties textile products made therefrom and method of imparting said improved properties
US3857727A (en) * 1970-10-22 1974-12-31 L Benisek Textile finishing
JPS5562832A (en) * 1978-11-06 1980-05-12 Asahi Chemical Ind Manufacture of fiber reinforced cement product
WO1984003275A1 (en) * 1983-02-23 1984-08-30 Courtaulds Plc Cellulose fibers for cement reinforcement
JPS60260449A (ja) * 1984-06-08 1985-12-23 帝人株式会社 セメント成型品
US4515636A (en) * 1984-08-17 1985-05-07 E. I. Du Pont De Nemours And Company Reinforced cement

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Polyfunctional Tyzor Organic Titanates, pp. 4, 5, 8, 17. *
Polyfunctional Tyzor® Organic Titanates, pp. 4, 5, 8, 17.
Processing of Composites with Titanate Coupling Agents A Review (Polymer Eng. & Sci.), Dec. 1984, vol. 24, No. 18, pp. 1369 1382. *
Processing of Composites with Titanate Coupling Agents-A Review (Polymer Eng. & Sci.), Dec. 1984, vol. 24, No. 18, pp. 1369-1382.

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5416156A (en) * 1988-10-14 1995-05-16 Revlon Consumer Products Corporation Surface coating compositions containing fibrillated polymer
US4994148A (en) * 1989-03-14 1991-02-19 Shetka Stanley J Pulp press molding method for making products from paper pulp from recycled paper
US4974522A (en) * 1989-06-09 1990-12-04 Relmech Manufacturing Limited Cold-molded cementitious composites reinforced with surface-modified polyamide fibres and method of preparing same
US5593625A (en) * 1992-08-11 1997-01-14 Phenix Biocomposites, Inc. Biocomposite material and method of making
US5635123A (en) 1992-08-11 1997-06-03 Phenix Biocomposites, Inc. Biocomposite material and method of making
US5616683A (en) * 1993-01-13 1997-04-01 Hoechst Ag Process for maintaining of improving the mechanical properties of fibers of aromatic copolyamides in alkaline media and shaped articles containing such fibers
US5611882A (en) * 1993-08-11 1997-03-18 Phenix Biocomposites, Inc. Board stock and method of manufacture from recycled paper
WO2000059812A1 (en) 1999-04-07 2000-10-12 Hudson-Sharp Machine Company Conveyor apparatus for conveying stacks of articles
WO2004020358A1 (en) * 2002-08-27 2004-03-11 Laticrete International, Inc. Cement-based thin-set mortar
US6784229B2 (en) 2002-08-27 2004-08-31 Laticrete International, Inc. Cement-based thin-set mortar
EP1546059A1 (en) * 2002-08-27 2005-06-29 Laticrete International, Inc. Cement-based thin-set mortar
EP1546059B1 (en) * 2002-08-27 2017-06-14 Laticrete International, Inc. Cement-based thin-set or medium bed or underlayment mortar or grout and method for setting tiles or for applying an underlayment mortar to a substrate

Also Published As

Publication number Publication date
AU585790B2 (en) 1989-06-22
CA1276087C (en) 1990-11-13
DK618286A (da) 1987-06-21
DK618286D0 (da) 1986-12-19
EP0227452A1 (en) 1987-07-01
JPS62158149A (ja) 1987-07-14
EP0227452B1 (en) 1990-03-21
DE3669705D1 (de) 1990-04-26
AU6673686A (en) 1987-06-25
KR870005928A (ko) 1987-07-08

Similar Documents

Publication Publication Date Title
US4693749A (en) Cement reinforcement
US4306911A (en) Method for the production of a fiber-reinforced hydraulically setting material
US4248664A (en) Fibrous sheet materials
US6010786A (en) Polypropylene fiber for reinforcing cement
US4199366A (en) Fiber-reinforced cement-like material
US4515636A (en) Reinforced cement
US5616683A (en) Process for maintaining of improving the mechanical properties of fibers of aromatic copolyamides in alkaline media and shaped articles containing such fibers
US5000824A (en) Polyethylene pulp
CA2555430A1 (en) Cementitious material reinforced with purified cellulose fiber
WO2010037628A1 (en) Fibre-cement product compositions and shaped products obtained therefrom
JPS6156180B2 (ja)
CA2017556C (en) Thin, resin-saturable aromatic polyamide paper and process for making same
US3985610A (en) Water-resistant asbestos-cement
GB2031043A (en) Fibrous Sheet Material
EP0264107A2 (en) Non-woven mat of continuous acrylic filaments showing a high modulus and manufactured articles reinforced by this mat
JP3282930B2 (ja) 無機質板及びその製造方法
JP3282920B2 (ja) 無機質板の製造方法
JPH07286401A (ja) 水硬性無機質抄造製品
JP3227234B2 (ja) 水硬性無機質成型製品
JP2721563B2 (ja) 水硬性成形用組成物
SU1098915A1 (ru) Состав защитного покрыти дл стекл нного волокна
SU1016335A1 (ru) Полимерна пресскомпозици
CA1146603A (en) Fibre - reinforcement cementitious product
SU618470A1 (ru) Состав дл получени волокнистого материала
JPH02259190A (ja) ホイスカー含有シート

Legal Events

Date Code Title Description
AS Assignment

Owner name: E. I. DU PONT DE NEMOURS AND COMPANY, WILMINGTON,

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:GALE, DAVID M.;REEL/FRAME:004499/0919

Effective date: 19851216

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12